EP2940703B1 - Séparateur pour condensateurs électriques à double couche et condensateur électrique à double couche - Google Patents

Séparateur pour condensateurs électriques à double couche et condensateur électrique à double couche Download PDF

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Publication number
EP2940703B1
EP2940703B1 EP13866727.4A EP13866727A EP2940703B1 EP 2940703 B1 EP2940703 B1 EP 2940703B1 EP 13866727 A EP13866727 A EP 13866727A EP 2940703 B1 EP2940703 B1 EP 2940703B1
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EP
European Patent Office
Prior art keywords
fibers
separator
double layer
electric double
layer capacitor
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EP13866727.4A
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German (de)
English (en)
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EP2940703A1 (fr
EP2940703A4 (fr
Inventor
Tomohiro Hayakawa
Hiroyuki Kawai
Hideo Hayashi
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Kuraray Co Ltd
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Kuraray Co Ltd
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/429—Natural polymers
    • H01M50/4295—Natural cotton, cellulose or wood
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/44—Fibrous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/04—Hybrid capacitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a separator for capacitor that is useful as a constituent material of an electric double layer capacitor, and to an electric double layer capacitor including the same separator.
  • Electric double layer capacitors have high capacitance of similar level as those of nickel-cadmium batteries, nickel-hydrogen batteries, and lithium ion batteries. Therefore, electric double layer capacitors have been recently used for memory backup power sources of personal computers, auxiliaries or alternatives to rechargeable batteries, in addition to conventional uses of capacitors in power smoothing or noise absorption.
  • Rechargeable batteries of conventional type had high capacitance, but had relatively short lifetime, and had difficulty in rapid charge-discharge.
  • the electric double layer capacitors have advantageous properties as capacitors such as long lifetime and rapid charge-discharge, in addition to relatively high capacitance.
  • an electric double layer capacitor is constituted of positive and negative electrodes, an electrolyte solution, a separator, current collectors, and others, where the separator is used for allowing passage of electrolyte solution while inhibiting electrical contact between the positive and negative electrodes. Since internal resistance of a separator increases with increasing thickness resulting in increasing length of the path between the electrodes, reduction of separator thickness by constituting the separator with extra-fine fibers is demanded.
  • Patent Document 1 discloses an electric double layer capacitor in which a pair of polarizing electrodes is separated by a separator, wherein the separator is prepared by producing a wet paper using cellulose as a raw material, and drying the wet paper while preserving porous structure of the wet paper.
  • Patent Document 1 JP Laid-open Patent Publication No. 10-256088 US 2003/096171 A1 (D1) describes a separator for electrochemical cell comprising a fiber sheet containing at least 10 weight % of polyvinyl alcohol fibers.
  • An object of the present invention is to provide a separator for an electric double layer capacitor, the separator having a low density, decreased thickness, and reduced electrical resistance.
  • Another object of the present invention is to provide a separator for an electric double layer capacitor, the separator allowing reduction of thickness while ensuring sufficient strength required for a separator for electric double layer capacitors.
  • Still other object of the invention is to provide a separator for an electric double layer capacitor, the separator having gas permeability (porous property, ion permeability) while ensuring sufficient strength required for a separator for an electric double layer capacitor.
  • the other object of the present invention is to provide a separator for an electric double layer capacitor, the separator having sufficient strength (e.g., tensile strength), thin thickness, low density, and gas permeability (porous property, ion permeability) in appropriate balance.
  • the inventors focused on polyvinyl alcohol fibers (polyvinyl alcohol-based fibers) having hot water-dissolving temperature in a specific range, and found that (ii) where a fiber sheet was prepared through wet process from polyvinyl alcohol fibers having hot water-dissolving temperature higher than 85°C and lower than 100°C, the polyvinyl alcohol fibers are in contact with each other on fiber surfaces at the crossing points of the fibers while maintaining properties as subject fibers, and that (iii) the thus obtained fiber sheet had low density, reduced thickness, and could suppress increase of resistance where the sheet was used as a separator for electric double layer capacitor. Based on the above-described findings, the inventors conducted the present invention.
  • a first aspect of the present invention is a separator for an electric double layer capacitor, comprising a fiber sheet (made of a material) containing polyvinyl alcohol fibers (fibers A) having a hot water-dissolving temperature of lower than 100°C and higher than 85°C in a proportion of not less than 10% by mass based on the 100% by mass of the fiber sheet, the separator having a density within a range of 0.25 to 0.7 g/cm 3 and a thickness of not less than 5 ⁇ m and less than 40 ⁇ m.
  • the fiber sheet of the above-described separator for an electric double layer capacitor further contains polyvinyl alcohol fibers (fibers B) having hot water-dissolving temperature of lower than 80°C.
  • the fiber sheet is made of raw fibers that include the fibers A or both of the fibers A and fibers B, and further include cellulose fibers.
  • the cellulose fibers are beaten materials composed of organic solvent-spun cellulose fibers or natural cellulose fibers.
  • the above-described separator satisfies the following conditions 1 and 2.
  • a second aspect of the present invention is an electric double layer capacitor that comprises the above-described separator for an electric double layer capacitor.
  • the fiber sheet constituting the separator for an electric double layer capacitor contains not less than 10% by mass (relative to the total mass of the fiber sheet) of polyvinyl alcohol fibers (fibers A) having hot water-dissolving temperature of lower than 100°C and higher than 85°C, the fibers forming the fiber sheet are adhered to each other at the crossing points of the fibers while maintaining fiber forms. Therefore, it is possible to achieve a fiber sheet that has reduced thickness while maintaining strength property of the fibers, and also has gas permeability (ion permeability) resulting in low density and low resistance due to the presence of void space between fibers. Such a fiber sheet is specifically effective as a separator.
  • fibers B having a hot water-dissolving temperature lower than that of the fibers A are added to the fibers A to form the sheet, it is possible to strengthen the adhesion at the crossing points of fibers by binder effect exerted by the fibers B.
  • the addition of fibrillated fibers provides bonding in the fiber sheet by entanglement of fibers, and thereby improving flexibility of the sheet and providing shielding property of appropriate level to the sheet.
  • the fiber sheet has balanced thickness and mechanical strength.
  • an electric double layer capacitor equipped with the separator according to the first aspect of the present invention having the above-described properties, it is possible to decrease the thickness of the separator while decreasing the density of the separator, thereby decreasing distance between the electrodes and reducing resistance.
  • the present invention encompasses any combinations of at least two constitutions described in claims and/or specification. Specifically, the present invention encompasses any combinations of two or more claims.
  • a separator for an electric double layer capacitor of the present invention comprises a fiber sheet containing 10% by mass or more (relative to 100% by mass of the fiber sheet) of polyvinyl alcohol fibers (fibers A) having a hot water-dissolving temperature of lower than 100°C and higher than 85°C, the separator having a density within a range of 0.25 to 0.7 g/cm 3 , and having a thickness of not less than 5 ⁇ m and less than 40 ⁇ m.
  • polyvinyl alcohol fibers (fibers A) having a hot water-dissolving temperature of lower than 100°C and higher than 85°C must be blended in an amount of 10% by mass or more (preferably 15% by mass or more, more preferably 25% by mass or more).
  • Upper limit of the amount of fibers A is not limited provided that a fiber sheet can be formed. Typically, the upper limit may be about 70% by mass (preferably, 60% by mass).
  • the hot water-dissolving temperature is lower than 100°C
  • moisture in the fibers can allow surfaces of the fibers to be adhered with each other at the crossing points of the fibers during heating and drying process, while maintaining the fiber structure so as to achieve formation of a sheet.
  • the hot water-dissolving temperature is 100°C or higher
  • the hot water-dissolving temperature is not higher than 85°C
  • polyvinyl alcohol constituting the fibers is completely melted or dissolved during heating and drying the wet-formed web.
  • the fiber sheet is formed by using polyvinyl alcohol fibers having hot water-dissolving temperature of lower than 98°C and higher than 90°C.
  • the hot water-dissolving temperature denotes a value that is measured in accordance with the method described in the below described Examples.
  • the present invention is characterized by forming a sheet using polyvinyl alcohol fibers (fibers A) having a hot water-dissolving temperature within a specific range. Since the polyvinyl alcohol fibers having the hot water-dissolving temperature in a specific range can adhere to each other at the crossing points by heating during forming the fiber sheet, the fibers function as binder fibers as well as functioning as subject fibers of the sheet.
  • the polyvinyl alcohol fibers having a hot water-dissolving temperature of lower than 100°C and higher than 85°C may be obtained from a vinyl alcohol polymer having an average degree of polymerization of 1000 to 5000, and a degree of saponification of not lower than 95% by mole, where the average degree of polymerization is a viscosity average degree of polymerization determined based on the viscosity of aqueous solution of 30°C.
  • the vinyl alcohol polymer may be copolymerized with the other copolymer component. Based on the consideration of fiber forming ability and mechanical properties of the formed fibers, it is preferable to control the amount of copolymer component to be 20% by mole or less, preferably 10% by mole or less.
  • the vinyl alcohol polymer is escaped from crosslinking treatment or acetalizing treatment such as formalization (FA) or the like so as to maintain adherence between the fibers in the time of forming the fiber sheet. It is not necessary to compose the polyvinyl alcohol fibers only of the vinyl alcohol polymer, and the fibers may contain other polymer.
  • the polyvinyl alcohol fibers may be fibers that are spun only from vinyl alcohol polymer.
  • the fibers may be blend spun fibers or conjugated spun fibers (islands in a sea fiber type) with other type(s) of polymer(s) within a range in that the fibers have a predetermined hot water-dissolving temperature.
  • polyvinyl alcohol fibers since the polyvinyl alcohol fibers are desired to have high strength, polyvinyl alcohol fibers containing 80% by mass or more of vinyl alcohol polymer is preferred.
  • Spinning method for forming the fibers may be any of wet method (for example, using sodium sulfate bath, an alkali bath, or an organic solvent bath), dry method, or dry-wet method.
  • the fibers may be subjected to heat drawing (wet-heat drawing or dry-heat drawing), heat setting, or the like.
  • heat drawing wet-heat drawing or dry-heat drawing
  • heat setting heat setting
  • the polyvinyl alcohol fiber having a specific hot water-dissolving temperature may be available as products on the market, for example, under the name of "VN20200" manufactured by KUARAY CO., LTD.
  • single fiber fineness (fineness) of the fiber is 3.3 dtex or less, more preferably 1.1 dtex or less, even more preferably 0.8 dtex or less, based on the consideration of separativity and thickness reduction.
  • the fineness is preferably 0.01 dtex or more, more preferably 0.1 dtex or more so as to ensure paper making property and to suppress increase of internal pressure.
  • Fiber length may be determined to appropriate value in accordance with the single fiber fineness. Based on the consideration of paper making property or the like, the fiber length is preferably from 0.5 to 10 mm, more preferably from 1 to 5 mm.
  • the fiber sheet in order to further strengthen the adherence between the fibers and to enhance the performance of the fiber sheet, in addition to the above-described fibers A, the fiber sheet preferably contains polyvinyl alcohol fibers (fibers B: hereafter also referred to as polyvinyl alcohol binder) that have a hot water-dissolving temperature of lower than 80°C and binder performance (ability to provide adherence between fibers A in a molten or dissolved state by heating during or after fiber sheet formation by wet forming method).
  • fibers B hereafter also referred to as polyvinyl alcohol binder
  • Hot water-dissolving temperature of the polyvinyl alcohol binder fiber that suits the fibers B is preferably higher than 60°C and lower than 80°C, more preferably higher than 70°C and lower than 80°C.
  • fibers constituted from vinyl alcohol polymer having an average degree of polymerization of ca. 500 to 300, and a degree of saponification of 80 to 99% by mole (preferably 95 to 99% by mole) may be preferably used.
  • the polyvinyl alcohol fibers may be fibers that are spun only from vinyl alcohol polymer.
  • the fibers may be conjugate spun fibers or blend spun fibers (islands in a sea fibers) with other type(s) of polymer(s) within a range in that the fibers have a predetermined hot water-dissolving temperature. It is preferable to use polyvinyl alcohol fibers containing 30% by mass or more, preferably 50% by mass or more, and more preferably 80% by mass or more of vinyl alcohol polymer so as to ensure absorbability of electrolyte solution and mechanical property.
  • polyvinyl alcohol fibers having the above-described hot water-dissolving temperature may be produced by spinning the fibers in accordance with the same manner as the above-described fibers A, and subsequently drawing and/or setting the fibers in which the heat drawing and/or heat setting is (are) carried out in a smaller degree than those of fibers A.
  • single fiber fineness of the fiber is ca. 0.01 to 3 dtex and the fiber length is 1 to 5 mm based on the consideration of dispersibility in water, adherence with other components, pore size or the like.
  • the polyvinyl alcohol binder fiber is provided on the market by KURARY CO., LTD. under the name of "VPB101", "VPB041" or the like.
  • the amount of fibers B is preferably contained in an amount of 3 to 20% by mass relative to total mass of the fiber sheet. Too much amount of fibers B is not preferred since pores between the subject fibers are blocked (filled), resulting in reduction of gas permeability.
  • the fibers A and fibers B are used in combination, the fibers A preferably have a smaller fineness than the fineness of fibers B.
  • Cellulose fibers may be added to form the fiber sheet of the present invention.
  • the cellulose fibers may be selected from organic solvent spun cellulose fibers obtained by spinning cellulose dissolved in an organic solvent such as amine oxide, regenerated cellulose fibers, natural cellulose fibers such as various wood pulps or cotton linters, and marcelized or beaten materials thereof. Specifically, beaten fibers of organic solvent spun cellulose fibers or beaten fibers of natural cellulose fibers are preferred since the presence of fibrillated fibers allows the fiber sheet to form a network structure.
  • degree of beating shown by Canadian standard freeness is preferably ca. 0 to 130 mL, more preferably 0 to 110 mL, and further preferably 0 to 100 mL where the degree of beating is determined by a method described in the below described Examples.
  • the entanglement of fibrillated fibers is introduced into the fiber sheet by adding the above-described cellulose fibers to the fibers containing fiber A and optionally containing fiber B, it is possible to obtain a fiber sheet having flexibility and shielding property.
  • separators Conventionally, papers consisting only of cellulose fibers have been used as separators for capacitors. Those separators included a problem in that formation of dense sheet for obtaining predetermined strength resulted in reduction of gas permeability.
  • the present invention it is possible to form a separator having balanced mechanical property, thickness, gas permeability, resistance or the like, by using specific polyvinyl alcohol fibers as subject fibers constituting the separator.
  • the properties of the separator may be improved by providing flexibility and shielding property to the sheet by further adding cellulose fibers to the sheet.
  • the fiber sheet preferably contains less than 70% by mass, more preferably less than 60% by mass, and more preferably less than 50% by mass of the cellulose fibers.
  • a separator of the present invention may be formed, for example, as a wet-laid nonwoven fabric using the above-described fibers A, preferably further added with the fibers B and/or the cellulose fibers.
  • a method for forming the wet-laid nonwoven fabric is not particularly limited. For example, it is possible to achieve designated wet-laid nonwoven fabrics effectively by using a common wet paper machine.
  • a cylindrical net, a tanmo net (short net), and a Fourdrinier net may be used as a wire cloth.
  • a single layer sheet may be formed by using a single wire cloth selected from the above described wire clothes.
  • a fiber sheet having a plurality of layers may be formed by using a plurality of wire clothes in combination.
  • Heating for drying the sheet may be performed within a range of (TA + 15) to (TA + 55)°C, preferably within a range of (TA + 25) to (TA + 45)°C, where TA denotes the hot water-dissolving temperature of fiber A.
  • conditions for heat pressing of the fiber sheet are controlled within a range that allows the fiber sheet to retain gas permeability.
  • the heat pressing may be performed at a temperature of 150 to 250°C and a linear pressure of 75 to 150 kgf/cm.
  • absorbability of electrolyte solution as a separator may be improved by hydrophilic treatment of the obtained sheet, for example, by surfactant treatment.
  • the separator As a separator for electric double layer capacitors, the separator is required to have a low density within a range of 0.25 to 0.7 g/cm 3 so as to suppress the resistance. In addition, it is preferable that the separator has tensile strength (in a longitudinal direction of the fiber sheet) required to pass the working process to attach the separator to the electric double layer capacitor. Preferably, the separator has sufficient porosity (gas permeability) to ensure ion permeability.
  • the separator may have a density within a range of 0.3 to 0.6 g/cm 3 , more preferably 0.35 to 0.5 g/cm 3 .
  • the separator has a small thickness such that relatively large amount of electrode material can be filled in a predetermined volume.
  • strength conflicts with the gas permeability and small thickness.
  • the fiber sheet according to the present invention is formed using polyvinyl alcohol fibers having a hot water-dissolving temperature of 85 to 100°C, the fibers are adhered to each other at the crossing points while maintaining the fiber structure. Therefore, as an effect of high strength property of the polyvinyl alcohol fibers, it is possible to achieve a thin fiber sheet having desired performance with small mass per unit area.
  • the thickness of the separator may be in the range of not less than 5 ⁇ m and less than 40 ⁇ m, preferably within a range of 5 to 30 ⁇ m, more preferably within a range of 10 to 30 ⁇ m.
  • the basis weight (mass per unit area) of the separator may be controlled to arbitrary value depending on the thickness of the separator.
  • the separator may have a basis weight of 5 to 20 g/m 2 , preferably 7 to 18 g/m 2 , more preferably 8 to 15 g/m 2 .
  • gas permeability of the separator may be 1.5 to 35 cc/cm 2 /s, and preferably 2 to 30 cc/cm 2 /s, where the gas permeability denotes a value measure in the method as described in Example.
  • a ratio of the tensile strength (kg/15 mm) in a longitudinal direction of the fiber sheet and the thickness ( ⁇ m) of the separator preferably satisfy the below described formula.
  • the separator according to the present invention can satisfy the conditions shown by the below formula.
  • the ratio shown in the above described formula is preferably larger than 0.03.
  • An electric double layer capacitor that utilizes the separator according to the present invention at least comprises positive and negative electrodes, an electrolyte solution, the above-described separator, and current collectors.
  • the electric double layer capacitor may further comprise other member(s) commonly used in the technical field of electric double layer capacitors.
  • the electric double layer capacitor may at least comprise: an element that is constituted of a separator, and a pair of negative and positive polarizing electrodes that are opposed to each other via the separator and form polarized electrode layer on the current collector; and a case that houses the element and an electrolyte solution.
  • a form of the electric double layer capacitor of the present invention is not particularly limited.
  • the electric double layer capacitor may have various forms, for example, coin type form, wound-type form, or the like.
  • a polarized electrode of positive electrode side and a polarized electrode of negative electrode side are each formed on a current collector composed of a metallic material, and these polarized electrodes are separated by a separator.
  • DC voltage is applied to a pair of solid electrodes immersed in a solution containing electrolyte ions
  • negative ions are electrostatically attracted to the positively polarized electrode
  • positive ions are electrostatically attracted to the negatively polarized electrode, forming the electric double layer in each of the interfaces between the electrodes and the electrolyte solution.
  • Species of positive and negative electrodes in the capacitor, and species of electrolytes solution are not particularly limited, and may be selected from those conventionally used in electric double layer capacitors.
  • the separator of the present invention may be used in a lithium ion capacitor that comprises a positive electrode of electric double layer and a negative electrode (for example, carbonaceous material that can store lithium ions) of a lithium ion rechargeable battery. Since the principle of an electric double layer capacitor is applied in lithium ion capacitors, the category of the electric double layer capacitor in the description of the present invention may include the lithium ion capacitors.
  • the separator of the present invention is specifically applicable to a separator of an electric double layer capacitor that comprises: carbonaceous positive and negative electrodes; and a non-aqueous organic-based electrolyte solution (electrolyte solution in which a salt of tetraalkylammonium cations and anions such as BF 4 - , PF 6 - , SO 3 CF 3 - , AsF 6 - , N(SO 2 CF 3 ) 2 - , and ClO 4 - is dissolved in an organic solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, sulfolane, and methyl sulfolane).
  • a non-aqueous organic-based electrolyte solution electrolyte solution in which a salt of tetraalkylammonium cations and anions such as BF 4 - , PF 6 - , SO 3 CF
  • test sample was prepared by attaching a spindle to a polyvinyl alcohol fiber tow of 5 cm in length in a load of 0.9 gf/500 dtex.
  • the test sample was suspended in water of 500 cc (20°C), and the hot water-dissolving temperature was determined as a temperature at which the fiber tow was dissolved down during heating the water at a heating rate of 1°C per minute.
  • Each test sample having a dimension of 100 mm x 100 mm was obtained from a specimen along the longitudinal direction. Mass of the sample was measure at moisture equilibrium state, and the measured value was converted to mass per 1 m 2 .
  • Thickness and density of each specimen were measured in accordance with JIS P 8118 "Paper and board - Determination of thickness and density”.
  • Tensile strength (kg/15 mm) of each fiber sheet along the longitudinal direction was measured in accordance with JIS P8113 "Paper and board - Determination of tensile properties”.
  • EC ethtyl carbonate
  • EMC ethyl methyl carbonate
  • the specimen at a state sufficiently retaining the solution was subjected to measurement of impedance at ambient conditions of 20°C and 65% using an impedance measurement device (KC-547 LCR METER) manufactured by KOKUYO ELECTRIC CO.,LTD.
  • an impedance measurement device KC-547 LCR METER manufactured by KOKUYO ELECTRIC CO.,LTD.
  • the first fibers were non-formalized polyvinyl alcohol (PVA) fibers (VN20200 manufactured by KURARAY CO., Ltd.) having a hot water-dissolving temperature of 95°C, fineness of 0.3 dtex, and fiber length of 2 mm
  • the second fibers were polyvinyl alcohol fibers (VPB101 manufactured by KURARAY CO., Ltd.) having a hot water-dissolving temperature of 72°C, fineness of 1.1 dtex, and fiber length of 3 mm
  • the third fibers were fibrillated fibers having CSF of 10 mL that were prepared by beating solvent spun cellulose fibers (TENCEL, a registered trademark, manufactured by Lenzing AG) having fineness of 1.7 dtex and fiber length of 3 mm using a pulper and a fiberizer.
  • a slurry was prepared by mixing the first, second, and third constituent fibers with a mixing ratio shown in Table 1.
  • a fiber sheet was prepared by laying a web using a cylinder type paper machine, drying the wet-laid web at a temperature of 130°C using a dryer, and pressing the dried web using a heat press device with a linear pressure of 100 kgf/cm at a temperature of 200°C to form a sheet. Physical properties of the obtained sheet are shown in Table 2.
  • Sheets were obtained in accordance with the similar manner as in Example 1 except for controlling mixing ratio of the constituent fibers 1, 2, and 3 to be values shown in Table 1. Properties of the obtained sheet are shown in Table 2.
  • a slurry was prepared by mixing the constituent fibers 1, 2, and 3 similar to those of Example 1 with the same mixing ratio.
  • fiber sheet was obtained by wet-laying a web, drying the wet-laid web using a dryer, and pressing the web using a heat press device to obtain a sheet having a basis weight of 10 g/m 2 , a thickness of 20 ⁇ m, and a density of 0.50 g/m 3 , where the thickness was controlled by controlling a clearance of the heat press device. Properties of the obtained sheet are shown in Table 2.
  • a slurry was prepared by mixing the constituent fibers 1, 2, and 3 similar to those of Example 1 with the same mixing ratio.
  • fiber sheet was obtained by wet-laying a web, drying the wet-laid web using a dryer, and pressing the dried web using a heat press device to obtain a sheet having a mass per unit area of 9 g/m 2 , a thickness of 25 ⁇ m, and a density of 0.36 g/m 3 , where the thickness was controlled by controlling a clearance of the heat press device. Properties of the obtained sheet are shown in Table 2.
  • a sheet was prepared in accordance with the similar manner as in Example 1 except for controlling mixing ratio of the constituent fibers 1, 2, and 3 to be values shown in Table 1. Properties of the obtained sheet are shown in Table 2.
  • Sheets were prepared in accordance with the similar manner as in Example 1 except for controlling mixing ratios of the constituent fibers 1, 2, and 3 to be values shown in Table 1. Properties of the obtained sheets are shown in Table 2.
  • a slurry was prepared by mixing the constituent fibers 1, 2, and 3 similar to those of Example 1 with the same mixing ratio.
  • fiber sheet was obtained by wet-laying a web, drying the wet-laid web using a dryer, and pressing the dried web using a heat press device to obtain a sheet having a mass per unit area of 11 g/m 2 , a thickness of 13 ⁇ m, and a density of 0.85 g/m 3 , where the thickness was controlled by controlling a clearance of the heat press device. Properties of the obtained sheet are shown in Table 2.
  • Polyvinyl alcohol (PVA) fibers (VN30200 manufactured by KURARAY CO.,LTD.) having a hot water-dissolving temperature higher than 100°C was used as an alternative to constituent fibers 1 of Example 1, and fibrillated fibers (CSF 150 mL) prepared by beating solvent spun cellulose fibers (TENCEL, a registered trademark, manufactured by Lenzing AG) having fineness of 1.7 dtex and fiber length of 3 mm using a disk refiner were used as an alternative to constituent fibers 3 of Example 1. Except for the use of these alternative fibers and their mixing ratio with the constituent fibers 2 as shown in Table 1, a sheet was obtained in the similar manner as in Example 1. Properties of the obtained sheet are shown in Table 2.
  • a sheet was prepared in accordance with the similar manner as in Example 1 except for using fibrillated fibers (CSF 150 mL) prepared by beating solvent spun cellulose fibers (TENCEL, a registered trademark, manufactured by Lenzing AG) having fineness of 1.7 dtex and fiber length of 3 mm using a disk refiner as an alternative to constituent fibers 3 of Example 1. Properties of the obtained sheets are shown in Table 2.
  • CSF 150 mL fibrillated fibers
  • TENCEL a registered trademark, manufactured by Lenzing AG
  • a sheet was prepared in accordance with the similar manner as in Example 1 except for using polyvinyl alcohol (PVA) based fibers (VN30200 manufactured by KURARAY CO.,LTD.) having a hot water-dissolving temperature higher than 100°C as an alternative to constituent fibers 1 of Example 1. Properties of the obtained sheets are shown in Table 2.
  • PVA polyvinyl alcohol
  • Example 1 Specific constitutions of the constituent fibers of the sheets of Examples 1 to 6 and Comparative Examples 1 to 6 are shown in Table 1, and properties of each sheet (tensile strength, gas permeability, resistance, a ratio of tensile strength/ thickness) are shown in Table 2.
  • Table 1 Example 1
  • Example 2 Example 3
  • Example 4 Example 5
  • Example 6 Comp. 1 Comp. 2 Comp. 3 Comp.
  • the separator for electric double layer capacitor of the present invention it is possible to achieve reduction of thickness and density of separator. Since electric double layer capacitors having such separators have improved performance, the separator has industrial applicability.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Nonwoven Fabrics (AREA)
  • Paper (AREA)

Claims (7)

  1. Séparateur pour condensateur électrique à double couche comprenant une feuille de fibres contenant 10 % en masse ou plus, par rapport à 100 % en masse de la feuille de fibres, de fibres de polyalcool vinylique (fibres A) présentant une température de dissolution dans l'eau chaude inférieure à 100 °C et supérieure à 85 °C, le séparateur présentant une masse volumique située dans une plage allant de 0,25 à 0,7 g/cm3, et une épaisseur située dans une plage allant de pas moins de 5 µm à moins de 40 µm.
  2. Séparateur pour condensateur électrique à double couche selon la revendication 1, dans lequel la feuille de fibres contient en outre des fibres de polyalcool vinylique (fibres B) présentant une température de dissolution dans l'eau chaude inférieure à 80 °C en plus des fibres A.
  3. Séparateur pour condensateur électrique à double couche selon la revendication 2, dans lequel le rapport en masse entre les fibres A et les fibres B satisfait A/B = 40/60 à 99/1.
  4. Séparateur pour condensateur électrique à double couche selon l'une quelconque des revendications 1 à 3, dans lequel la feuille de fibres contient en outre des fibres de cellulose.
  5. Séparateur pour condensateur électrique à double couche selon la revendication 4, dans lequel les fibres de cellulose sont des fibres battues de fibres de cellulose filées avec un solvant organique ou de fibres de cellulose naturelle.
  6. Séparateur pour condensateur électrique à double couche selon l'une quelconque des revendications 1 à 5, dans lequel le séparateur satisfait les conditions suivantes :
    premièrement, une épaisseur du séparateur est située dans une plage allant de 5 à 30µm; et
    deuxièmement, la résistance du séparateur dans une direction longitudinale (kg/15 mm)/épaisseur du séparateur (µm) est supérieure à 0,025.
  7. Condensateur électrique à double couche comprenant un séparateur pour condensateur électrique à double couche selon l'une quelconque des revendications 1 à 6.
EP13866727.4A 2012-12-26 2013-12-24 Séparateur pour condensateurs électriques à double couche et condensateur électrique à double couche Active EP2940703B1 (fr)

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JP2012283132 2012-12-26
PCT/JP2013/084436 WO2014103992A1 (fr) 2012-12-26 2013-12-24 Séparateur pour condensateurs électriques à double couche et condensateur électrique à double couche

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JP7250801B2 (ja) 2017-09-26 2023-04-03 エスヴェーエム ルクセンブルク 制御された細孔径を有するアルカリ電池セパレーター
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CN111048315B (zh) * 2019-12-26 2021-08-27 东莞东阳光科研发有限公司 叠片铝电解电容制造方法及用该方法制作的电容器

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Also Published As

Publication number Publication date
WO2014103992A1 (fr) 2014-07-03
JPWO2014103992A1 (ja) 2017-01-12
EP2940703A1 (fr) 2015-11-04
CN104885173B (zh) 2018-03-02
EP2940703A4 (fr) 2016-09-07
KR20150100769A (ko) 2015-09-02
US20150294801A1 (en) 2015-10-15
US10020124B2 (en) 2018-07-10
JP6129209B2 (ja) 2017-05-17
KR101827617B1 (ko) 2018-02-08
CN104885173A (zh) 2015-09-02

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